Chiral thiouronium salts: synthesis, characterisation and application in NMR enantio-discrimination of chiral oxoanions

Chiral thioureas and functionalised chiral thiouronium salts were synthesised starting from the relatively cheap and easily available chiral amines: (S)-methylbenzylamine and rosin-derived (+)-dehydroabietylamine. The introduction of a delocalised positive charge to the thiourea functionality, by an alkylation reaction at the sulfur atom, enables dynamic rotameric processes: hindered rotations about the delocalised CN and CS bonds. Hence, four different rotamers/isomers may be recognised: syn-syn, syn-anti, anti-syn and anti-anti. Extensive H-1 and C-13 NMR studies have shown that in hydrogen-bond acceptor solvents, such as perdeuteriated dimethyl sulfoxide, the syn-syn conformation is preferable. On the other hand, when using non-polar solvents, such as CDCl3, the mixture of syn-syn and syn-anti isomers is detectable, with an excess of the latter. Apart from this, in the case of S-butyl-N,N'-bis(dehydroabietyl)thiouronium ethanoate in CDCl3, the H-1 NMR spectrum revealed that strong bifurcated hydrogen bonding between the anion and the cation causes global rigidity without signs of hindered rotamerism observable on the NMR time scale. This suggested that these new salts might be used as NMR discriminating agents for chiral oxoanions, and are indeed more effective than their archetypal guanidinium analogues or the neutral thioureas. The best results in recognition of a model substrate, mandelate, were obtained with S-butyl-N,N'-bis(dehydroabietyl) thiouronium bistriflamide. It was confirmed that the chiral recognition occurred not only for carboxylates but also for sulfonates and phosphonates. Further H-1 NMR studies confirmed a 1 : 1 recognition mode between the chiral agent (host) and the substrate (guest); binding constants were determined by H-1 NMR titrations in solutions of DMSO-d(6) in CDCl3. It was also found that the anion of the thiouronium salt had a significant influence on the recognition process: anions with poor hydrogen-bond acceptor abilities led to the best discrimination. The presence of host-guest hydrogen bonding was confirmed in the X-ray crystal structure of S-butyl-N,N'-bis(dehydroabietyl)thiouronium bromide and by computational studies (density functional theory).

Behavioural context of multi-scale species distribution models assessed by radio-tracking

Incorporating ecological processes and animal behaviour into Species Distribution Models (SDMs) is difficult. In species with a central resting or breeding place, there can be conflict between the environmental requirements of the 'central place' and foraging habitat. We apply a multi-scale SDM to examine habitat trade-offs between the central place, roost sites, and foraging habitat in . Myotis nattereri. We validate these derived associations using habitat selection from behavioural observations of radio-tracked bats. A Generalised Linear Model (GLM) of roost occurrence using land cover variables with mixed spatial scales indicated roost occurrence was positively associated with woodland on a fine scale and pasture on a broad scale. Habitat selection of radio-tracked bats mirrored the SDM with bats selecting for woodland in the immediate vicinity of individual roosts but avoiding this habitat in foraging areas, whilst pasture was significantly positively selected for in foraging areas. Using habitat selection derived from radio-tracking enables a multi-scale SDM to be interpreted in a behavioural context. We suggest that the multi-scale SDM of . M. nattereri describes a trade-off between the central place and foraging habitat. Multi-scale methods provide a greater understanding of the ecological processes which determine where species occur and allow integration of behavioural processes into SDMs. The findings have implications when assessing the resource use of a species at a single point in time. Doing so could lead to misinterpretation of habitat requirements as these can change within a short time period depending on specific behaviour, particularly if detectability changes depending on behaviour. © 2011 Gesellschaft für ökologie.

Field Measurements of a Full Scale Tidal Device

Field testing studies are required for tidal turbine device developers to determine the performance of their turbines in tidal flows. Full-scale testing of the SCHOTTEL tidal turbine has been conducted at Queen’s University Belfast’s tidal site at Strangford Lough, NI. The device was mounted on a floating barge. Testing was conducted over 48 days, for 288 h, during flood tides in daylight hours. Several instruments were deployed, resulting in an expansive data set. The performance results from this data set are presented here. The device, rated to 50 kW at 2.75 m/s was tested in flows up to 2.5 m/s, producing up to 19 kW, when time-averaged. The thrust on the turbine reached 17 kN in the maximum flow. The maximum system efficiency of the turbine in these flows reached 35%. The test campaign was very successful and further tests may be conducted at higher flow speeds in a similar tidal environment.

Multiphysics Simulation of Thermal Plasma Produced by Lightning Strike on Aircraft Structures

A novel numerical technique is proposed to model thermal plasma of microseconds/milliseconds time-scale effect. Modelling thermal plasma due to lightning strike will allow the estimation of electric current density, plasma pressure, and heat flux at the surface of the aircraft structure. These input data can then be used for better estimation of the mechanical/thermal induced damage on the aircraft structures for better protection systems design. Thermal plasma generated during laser cutting, electric (laser) welding and other plasma processing techniques have been the focus of many researchers. Thermal plasma is a gaseous state that consists from a mixture of electrons, ions, and natural particles. Thermal plasma can be assumed to be in local thermodynamic equilibrium, which means the electrons and the heavy species have equal temperature. Different numerical techniques have been developed using a coupled Navier Stokes – Heat transfer – Electromagnetic equations based on the assumption that the thermal plasma is a single laminar gas flow. These previous efforts focused on generating thermal plasma of time-scale in the range of seconds. Lighting strike on aircraft structures generates thermal plasma of time-scale of milliseconds/microseconds, which makes the previous physics used not applicable. The difficulty comes from the Navier-Stokes equations as the fluid is simulated under shock load, this introducing significant changes in the density and temperature of the fluid.

The geographical structure of British bird distributions:diversity, spatial turnover and scale

1. Using data on the spatial distribution of the British avifauna, we address three basic questions about the spatial structure of assemblages: (i) Is there a relationship between species richness (alpha diversity) and spatial turnover of species (beta diversity)? (ii) Do high richness locations have fewer species in common with neighbouring areas than low richness locations?, and (iii) Are any such relationships contingent on spatial scale (resolution or quadrat area), and do they reflect the operation of a particular kind of species-area relationship (SAR)?

2. For all measures of spatial turnover, we found a negative relationship with species richness. This held across all scales, with the exception of turnover measured as beta (sim).

3. Higher richness areas were found to have more species in common with neighbouring areas.

4. The logarithmic SAR fitted better than the power SAR overall, and fitted significantly better in areas with low richness and high turnover.

5. Spatial patterns of both turnover and richness vary with scale. The finest scale richness pattern (10 km) and the coarse scale richness pattern (90 km) are statistically unrelated. The same is true of the turnover patterns.

6. With coarsening scale, locations of the most species-rich quadrats move north. This observed sensitivity of richness 'hotspot' location to spatial scale has implications for conservation biology, e.g. the location of a reserve selected on the basis of maximum richness may change considerably with reserve size or scale of analysis.

7. Average turnover measured using indices declined with coarsening scale, but the average number of species gained or lost between neighbouring quadrats was essentially scale invariant at 10-13 species, despite mean richness rising from 80 to 146 species (across an 81-fold area increase). We show that this kind of scale invariance is consistent with the logarithmic SAR.

Ecotoxicological evaluation of pesticide mixtures

Neste trabalho o risco da aplicação de moluscicidas (metaldeído e metiocarbe) para o isópode terrestre Porcellionides pruinosus foi avaliado usando como parâmetros a mortalidade e biomarcadores de exposição. O tempo até à morte dos isópodes (após contacto com os moluscicidas) foi muito curto, especialmente no caso da exposição ao metiocarbe. Os vários biomarcadores revelaram-se úteis para a compreensão do modo de acção dos dois moluscicidas neste isópode, particularmente o efeito do carbamato metiocarbe na inibição da enzima acetilcolinesterase (AChE). Os efeitos de combinações binárias de três produtos de protecção das plantas (PPP) dimetoato, glifosato e espirodiclofeno foram avaliados testando o comportamento de evitamento de P. pruinosus, o sucesso reprodutivo do colêmbolo Folsomia candida e o crescimento das plantas Brassica rapa e Triticum aestivum, usando os dois modelos de referência de concentração de adição (CA) e acção independente (IA). O modelo MIXTOX foi usado para avaliar possíveis desvios (devido a interacções entre os pesticidas) dos dois modelos de referência. Os resultados obtidos permitem constatar que estes PPP quando aplicados segundo a dose recomendada não acarretam efeitos perniciosos para os organismos testados. Foi detectado sinergismo na mistura feita com glifosato e espirodiclofeno no isópode P. pruinosus e na mistura com glifosato e dimetoato na planta T. aestivum. Um ecossistema terrestre em pequena escala (“STEM”) foi desenvolvido, contendo um solo agrícola mediterrânico. Nestes STEM, minhocas (Eisenia andrei), P. pruinosus, B. rapa e “bait-lamina” foram incorporados no sentido de avaliar os efeitos da aplicação de dimetoato com espirodiclofeno e glifosato com dimetoato. A dose recomendada de aplicação dos PPP, quer na exposição individual quer nas misturas binárias não teve quaisquer efeitos nas espécies testadas. As minhocas foram sensíveis à aplicação conjunta de dimetoato com espirodiclofeno (10 vezes a dose recomendada) na sua distribuição vertical ao longo da coluna do STEM, e foi detectado sinergismo (i.e. mais minhocas escaparam do que a predição feita pelo modelo IA). Em todas as misturas binárias feitas com glifosato e dimetoato registou-se um decréscimo no consumo de “bait-lamina”, indicando sinergismo (menos “bait-lamina” consumidos que o esperado). Dos quatro biomarcadores (Catalase, AChE, GST e LPO) avaliados nos isópodes, verificaram-se diferenças significativas na actividade da enzima AChE (quando dimetoato foi aplicado no solo) e LPO (aumento da actividade devido à aplicação de glifosato e dimetoato).

Impact of carbon/nitrogen feeding strategy on polyhydroxyalkanoates production using mixed microbial cultures

Polyhydroxyalkanoates (PHA) production using mixed microbial cultures (MMC) requires a multi-stage process involving the microbial selection of PHA-storing microorganisms, typically operated in sequencing batch reactors (SBR), and an accumulation reactor. Since low-cost renewable feedstocks used as process feedstock are often nitrogen-deficient, nutrient supply in the selection stage is required to allow for microbial growth. In this context, the possibility to uncouple nitrogen supply from carbon feeding within the SBR cycle has been investigated in this study. Moreover, three different COD:N ratios (100:3.79, 100:3.03 and 100:2.43) were tested in three different runs which also allowed the study of COD:N ratio on the SBR performance. For each run, a synthetic mixture of acetic and propionic acids at an overall organic load rate of 8.5 gCOD L-1 d-1 was used as carbon feedstock, whereas ammonium sulfate was the nitrogen source in a lab-scale sequence batch reactor (SBR) with 1 L of working volume. Besides, a sludge retention time (SRT) of 1 d was used as well as a 6 h cycle length. The uncoupled feeding strategy significantly enhanced the selective pressure towards PHA-storing microorganisms, resulting in a two-fold increase in the PHA production (up to about 1.3 gCOD L-1). A high storage response was observed for the two runs with the COD:N ratios (gCOD:gN) of 100:3.79 and 100:3.03, whereas the lowest investigated nitrogen load resulted in very poor performance in terms of polymer production. In fact, strong nitrogen limitation caused fungi to grow and a very poor storage ability by microorganisms that thrived in those conditions. The COD:N ratio also affected the polymer composition, indeed the produced poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) showed a variable HV content (1-20 %, w/w) among the three runs, lessening as the COD:N increased. This clearly suggests the possibility to use the COD:N ratio as a tool for tuning polymer properties regardless the composition of the feedstock.

Multi-scale support vector algorithms for hot spot detection and modelling

The algorithmic approach to data modelling has developed rapidly these last years, in particular methods based on data mining and machine learning have been used in a growing number of applications. These methods follow a data-driven methodology, aiming at providing the best possible generalization and predictive abilities instead of concentrating on the properties of the data model. One of the most successful groups of such methods is known as Support Vector algorithms. Following the fruitful developments in applying Support Vector algorithms to spatial data, this paper introduces a new extension of the traditional support vector regression (SVR) algorithm. This extension allows for the simultaneous modelling of environmental data at several spatial scales. The joint influence of environmental processes presenting different patterns at different scales is here learned automatically from data, providing the optimum mixture of short and large-scale models. The method is adaptive to the spatial scale of the data. With this advantage, it can provide efficient means to model local anomalies that may typically arise in situations at an early phase of an environmental emergency. However, the proposed approach still requires some prior knowledge on the possible existence of such short-scale patterns. This is a possible limitation of the method for its implementation in early warning systems. The purpose of this paper is to present the multi-scale SVR model and to illustrate its use with an application to the mapping of Cs137 activity given the measurements taken in the region of Briansk following the Chernobyl accident.

Verbal ability, previous practice and load on short-term memory as determiners of differences in a complex learning task: an experimental study

Traditional psychometric theory and practice classify people according to broad ability dimensions but do not examine how these mental processes occur. Hunt and Lansman (1975) proposed a 'distributed memory' model of cognitive processes with emphasis on how to describe individual differences based on the assumption that each individual possesses the same components. It is in the quality of these components ~hat individual differences arise. Carroll (1974) expands Hunt's model to include a production system (after Newell and Simon, 1973) and a response system. He developed a framework of factor analytic (FA) factors for : the purpose of describing how individual differences may arise from them. This scheme is to be used in the analysis of psychometric tes ts . Recent advances in the field of information processing are examined and include. 1) Hunt's development of differences between subjects designated as high or low verbal , 2) Miller's pursuit of the magic number seven, plus or minus two, 3) Ferguson's examination of transfer and abilities and, 4) Brown's discoveries concerning strategy teaching and retardates . In order to examine possible sources of individual differences arising from cognitive tasks, traditional psychometric tests were searched for a suitable perceptual task which could be varied slightly and administered to gauge learning effects produced by controlling independent variables. It also had to be suitable for analysis using Carroll's f ramework . The Coding Task (a symbol substitution test) found i n the Performance Scale of the WISe was chosen. Two experiments were devised to test the following hypotheses. 1) High verbals should be able to complete significantly more items on the Symbol Substitution Task than low verbals (Hunt, Lansman, 1975). 2) Having previous practice on a task, where strategies involved in the task may be identified, increases the amount of output on a similar task (Carroll, 1974). J) There should be a sUbstantial decrease in the amount of output as the load on STM is increased (Miller, 1956) . 4) Repeated measures should produce an increase in output over trials and where individual differences in previously acquired abilities are involved, these should differentiate individuals over trials (Ferguson, 1956). S) Teaching slow learners a rehearsal strategy would improve their learning such that their learning would resemble that of normals on the ,:same task. (Brown, 1974). In the first experiment 60 subjects were d.ivided·into high and low verbal, further divided randomly into a practice group and nonpractice group. Five subjects in each group were assigned randomly to work on a five, seven and nine digit code throughout the experiment. The practice group was given three trials of two minutes each on the practice code (designed to eliminate transfer effects due to symbol similarity) and then three trials of two minutes each on the actual SST task . The nonpractice group was given three trials of two minutes each on the same actual SST task . Results were analyzed using a four-way analysis of variance . In the second experiment 18 slow learners were divided randomly into two groups. one group receiving a planned strategy practioe, the other receiving random practice. Both groups worked on the actual code to be used later in the actual task. Within each group subjects were randomly assigned to work on a five, seven or nine digit code throughout. Both practice and actual tests consisted on three trials of two minutes each. Results were analyzed using a three-way analysis of variance . It was found in t he first experiment that 1) high or low verbal ability by itself did not produce significantly different results. However, when in interaction with the other independent variables, a difference in performance was noted . 2) The previous practice variable was significant over all segments of the experiment. Those who received previo.us practice were able to score significantly higher than those without it. J) Increasing the size of the load on STM severely restricts performance. 4) The effect of repeated trials proved to be beneficial. Generally, gains were made on each successive trial within each group. S) In the second experiment, slow learners who were allowed to practice randomly performed better on the actual task than subjeots who were taught the code by means of a planned strategy. Upon analysis using the Carroll scheme, individual differences were noted in the ability to develop strategies of storing, searching and retrieving items from STM, and in adopting necessary rehearsals for retention in STM. While these strategies may benef it some it was found that for others they may be harmful . Temporal aspects and perceptual speed were also found to be sources of variance within individuals . Generally it was found that the largest single factor i nfluencing learning on this task was the repeated measures . What e~ables gains to be made, varies with individuals . There are environmental factors, specific abilities, strategy development, previous learning, amount of load on STM , perceptual and temporal parameters which influence learning and these have serious implications for educational programs .

Probe-level linear model fitting and mixture modeling results in high accuracy detection of differential gene expression

Affiliation: Institut de recherche en immunologie et en cancérologie, Université de Montréal

Influence of plant species and richness on pollutant removal in treatment wetlands

Les marais filtrants artificiels sont des écosystèmes recréés par l’homme dans le but d’optimiser l’épuration des eaux usées. Lors de la sélection d’espèces végétales pour la mise en place de ces marais filtrants, l’utilisation d’une polyculture ainsi que d’espèces indigènes non invasives est de plus en plus recommandée. Néanmoins, la plupart des marais filtrants existants sont des monocultures utilisant des plantes envahissantes, probablement à cause du manque d’évidences scientifiques sur les avantages de la diversité végétale et de la performance des espèces locales. Ainsi, les questions de recherche autour desquelles s’oriente ma thèse sont: Les polycultures présentent-elles un potentiel épuratoire aussi ou plus grand que les monocultures, et une espèce indigène est-elle aussi efficace et performante qu’une espèce exotique envahissante dans des marais filtrants ? Trois expériences ont été conduites afin de répondre à ces questions. J’ai d’abord testé l’influence de la richesse végétale sur l’élimination des polluants en deux dispositifs expérimentaux: 1) comparant deux espèces de plantes émergentes en monoculture ou combinées séquentiellement, et 2) évaluant la performance de quatre espèces flottantes plantées en monoculture par rapport à des associations de deux (avec toutes les combinaisons possibles) et de quatre espèces. Une troisième expérience a été réalisée afin de comparer l’efficacité épuratoire de l’haplotype européen envahissant du roseau commun (Phragmites australis) et de la sous-espèce locale non-invasive (P. australis subsp. americanus). La composition en espèces végétales a produit un effet notable sur la performance des marais filtrants. La comparaison des performances en mono- et en polyculture n’a pas permis de démontrer clairement les avantages de la diversité végétale pour l’élimination des polluants dans les marais filtrants. Toutefois, les marais filtrants plantés avec une combinaison d’espèces étaient aussi efficaces que les monocultures des espèces les plus performantes. La comparaison entre les deux sous-espèces de P. australis indiquent que la sous-espèce indigène pourrait remplacer le roseau exotique envahissant, évitant ainsi les potentiels risques environnementaux sans toutefois compromettre l’efficacité du traitement. Les résultats prometteurs de la sous-espèce indigène de P. australis doivent encore être testés dans des expériences à grande échelle avant d’utiliser largement cette espèce dans les marais filtrants. Nos résultats suggèrent que, dans des conditions où la performance des macrophytes disponibles est inconnue ou ne peut être déterminée, l’utilisation d’une combinaison d’espèces présente les meilleures chances d’accomplir le plus haut niveau possible d’élimination de polluants. De plus, même si la diversité végétale ne présente pas un avantage mesurable en termes d’efficacité épuratoire, celle-ci améliore la résilience des marais filtrants et leur résistance aux stress et aux maladies.

SCAPA (Spacially Addressable Protein Array) – a Novel Protein Array for the Differential Profiling of Ligand-receptor Induced Signalling

While protein microarray technology has been successful in demonstrating its usefulness for large scale high-throughput proteome profiling, performance of antibody/antigen microarrays has been only moderately productive. Immobilization of either the capture antibodies or the protein samples on solid supports has severe drawbacks. Denaturation of the immobilized proteins as well as inconsistent orientation of antibodies/ligands on the arrays can lead to erroneous results. This has prompted a number of studies to address these challenges by immobilizing proteins on biocompatible surfaces, which has met with limited success. Our strategy relates to a multiplexed, sensitive and high-throughput method for the screening quantification of intracellular signalling proteins from a complex mixture of proteins. Each signalling protein to be monitored has its capture moiety linked to a specific oligo ‘tag’. The array involves the oligonucleotide hybridization-directed localization and identification of different signalling proteins simultaneously, in a rapid and easy manner. Antibodies have been used as the capture moieties for specific identification of each signaling protein. The method involves covalently partnering each antibody/protein molecule with a unique DNA or DNA derivatives oligonucleotide tag that directs the antibody to a unique site on the microarray due to specific hybridization with a complementary tag-probe on the array. Particular surface modifications and optimal conditions allowed high signal to noise ratio which is essential to the success of this approach.

Can the dynamical impact of the stratosphere on the troposphere be described by large-scale adjustment to the stratospheric PV distribution?

Recent numerical experiments have demonstrated that the state of the stratosphere has a dynamical impact on the state of the troposphere. To account for such an effect, a number of mechanisms have been proposed in the literature, all of which amount to a large-scale adjustment of the troposphere to potential vorticity (PV) anomalies in the stratosphere. This paper analyses whether a simple PV adjustment suffices to explain the actual dynamical response of the troposphere to the state of the stratosphere, the actual response being determined by ensembles of numerical experiments run with an atmospheric general-circulation model. For this purpose, a new PV inverter is developed. It is shown that the simple PV adjustment hypothesis is inadequate. PV anomalies in the stratosphere induce, by inversion, flow anomalies in the troposphere that do not coincide spatially with the tropospheric changes determined by the numerical experiments. Moreover, the tropospheric anomalies induced by PV inversion are on a larger scale than the changes found in the numerical experiments, which are linked to the Atlantic and Pacific storm-tracks. These findings imply that the impact of the stratospheric state on the troposphere is manifested through the impact on individual synoptic-scale systems and their self-organization in the storm-tracks. Changes in these weather systems in the troposphere are not merely synoptic-scale noise on a larger scale tropospheric response, but an integral part of the mechanism by which the state of the stratosphere impacts that of the troposphere.

The spacing of orographic rainbands triggered by small-scale topography

A combination of idealized numerical simulations and analytical theory is used to investigate the spacing between convective orographic rainbands over the Coastal Range of western Oregon. The simulations, which are idealized from an observed banded precipitation event over the Coastal Range, indicate that the atmospheric response to conditionally unstable flow over the mountain ridge depends strongly on the subridge-scale topographic forcing on the windward side of the ridge. When this small-scale terrain contains only a single scale (l) of terrain variability, the band spacing is identical to l, but when a spectrum of terrain scales are simultaneously present, the band spacing ranges between 5 and 10 km, a value that is consistent with observations. Based on the simulations, an inviscid linear model is developed to provide a physical basis for understanding the scale selection of the rainbands. This analytical model, which captures the transition from lee waves upstream of the orographic cloud to moist convection within it, reveals that the spacing of orographic rainbands depends on both the projection of lee-wave energy onto the unstable cap cloud and the growth rate of unstable perturbations within the cloud. The linear model is used in tandem with numerical simulations to determine the sensitivity of the band spacing to a number of environmental and terrain-related parameters.